The invention relates to compositions based on polyoxymethylene, blends of polycarbonate with acrylonitrile-butadiene-styrene terpolymer, or functional acrylate resin and crosslinking agent, which are stabilized by addition of a compound of the class of 3,3,5,5-tetraalkyl-piperazin-2,6-dione, new compounds of this class, the use of the novel compounds as stabilizers for organic material against harmful effects of light, oxygen and/or heat, and organic material stabilized correspondingly.
Structure and numbering of of 3,3,5,5-tetraalkyl-piperazin-2,6-dione is as shown in the formula: 
with R being alkyl.
Preparation of some of the above compounds, specific derivatives thereof, and use of these compounds as stabilizers e.g. for polyethylene, polypropylene, nylon or ABS is shown by T. Yoshioka et al., Bull. Chem. Soc. Jap. 45, 1855-1860 (1972); Luston and Vass, Makromol. Chem., Macromol. Symp. (1989), 27; and in the documents U.S. Pat. No. 4,413,096; C.A.99:141068; C.A.96:104191; U.S. Pat. No. 3,969,316; U.S. Pat. No. 3,936,456; U.S. Pat. No. 3,928,357; U.S. Pat. No. 3,928,330; US-A-3920659; U.S. Pat. No. 3,919,234.
It has now been found, that certain compounds of the 3,3,5,5-tetraalkyl-piperazin-2,6-dione class are especially well suitable as stabilizers for polyoxymethylene, blends of polycarbonate with acrylonitrile-butadiene-styrene terpolymer, or coatings based on a functional acrylate resin and a crosslinking agent.
The invention therefore pertains to a composition comprising
(A) a synthetic organic polymer selected from the group consisting of polyoxymethylene, a blend of polycarbonate with acrylonitrile-butadiene-styrene terpolymer, and a coating system based on a functional acrylate resin and a crosslinking agent, and
(B) as stabilizer a compound of the formula I or II 
wherein p is from the range 1 to 10;
s is from the range 1 to 8;
when s is 1,
A is C1-C18alkyl; C2-C18alkyl which is substituted by NH2, hydroxy, halogen and/or OR10 or interrupted by xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 and/or xe2x80x94NR10xe2x80x94; or A is C1-C18alkyl substituted by xe2x80x94COOR11 or phenyl;
when s is 2,
A is C2-C10alkylene; C4-C12alkenylene; C3-C15alkylene substituted by one or more OH and/or interrupted by one or more oxygen, phenylene, C1-C4alkylphenylene, xe2x80x94COOxe2x80x94, xe2x80x94CONHxe2x80x94, 
when s is 3,
A is C3-C10alkantriyl; C3-C12alkantriyl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (IIIa)-(IIId) 
when s is 4,
A is C4-C10alkantetryl; C4-C12alkantetryl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (IVa)-(IVd) 
when s is 5,
A is C5-C10alkanepentayl; C5-C12alkanepentayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (Va)-(Vc) 
when s is 6,
A is C6-C10alkanehexayl; C6-C12alkanehexayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (VIa)-(VIf) 
when s is 7,
A is C7-C10alkaneheptayl; C7-C12alkaneheptayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (VIIa)-(VIId) 
when s is 8,
A is C8-C10alkaneoctayl; C8-C12alkaneoctayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (VIIIa)-(VIIIb) 
the index i is zero or 1;
R1, R2, R3 and R4, independently of each other, are C1-C4alkyl, or R1 and R2 or R3 and R4, together with the carbon atom to which they are bound, form a cyclopentyl or cyclohexyl ring;
R5 is hydrogen; C1-C18alkyl; oxyl; OH; CH2CN; C1-C18alkoxy; C5-C12cycloalkoxy; C3-C8alkenyl; C3-C8alkynyl; C7-C12phenylalkyl; C7-C15phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; C1-C15phenylalkoxy; C1-C15phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; or R5 is C1-C8alkanoyl; C3-C5alkenoyl; C1-C18alkanoyloxy; glycidyl; or a group xe2x80x94CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl;
R8 and R9, and R28, R29, R30, R31, R32 and R33, independently of each other, are C1-C4alkylene;
R10 is C1-C8alkyl, C1-C8alkanoyl, C5-C12cycloalkyl, C7-C15phenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C1-C4alkyl and C1-C4alkoxy; or R10 is C1-C8alkyl or C1-C8alkanoyl substituted by OH, C1-C12alkoxy and/or a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C1-C4alkyl and/or C1-C18alkoxy;
R11 is C1-C18alkyl; C2-C18alkyl which is substituted by NH2, NHR10, N(R10)2, nitro, hydroxy and/or C1-C18alkoxy; C3-C18alkenyl; C5-C12cycloalkyl; C5-C12cycloalkyl which is substituted by C1-C4alkyl and/or interrupted by xe2x80x94Oxe2x80x94;
R12, R13 and R14, independently of each other, are C2-C10alkylene; C3-C12alkylene substituted by OH and/or interrupted by oxygen, phenylene, C1-C4alkylphenylene, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; C4-C12alkenylene;
R15 and Rxe2x80x215, independently of each other, are is C2-C10alkylene; C3-C12alkylene substituted by OH and/or interrupted by oxygen, phenylene, C1-C4alkylphenylene, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R16 is C3-C10alkantriyl; C3-C12alkantriyl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R17 is C4-C10alkantetryl; C4-C12alkantetryl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R18 is C5-C10alkanepentayl; C5-C12alkanepentayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R19 is C6-C10alkanehexayl; C6-C12alkanehexayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
X is xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94N(R10)xe2x80x94;
X1, X2, X3, X4, X5, X6, X7 and X8, independently of each other, are xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94;
Y is xe2x80x94Oxe2x80x94 or a residue of the formula 
Z stands for halogen, NH2, NHR10, N(R10)2 or C1-C4alkoxy;
Z1 has one of the meanings given for Z or is xe2x80x94Xxe2x80x94Rxe2x80x215xe2x80x94XH and
Z2 is H or a residue of the formula 
Where one compound carries more than one group denoted with the same symbol, these groups may be the same or different within their defined meanings.
Alkylene, cycloalkylene or alkenylene residues may be bonded on different carbon atoms or on the same carbon atom thus embracing alkylidene, cycloalkylidene and alkenylidene, respectively.
All residues, where appropriate, may be straight chain or branched unless otherwise indicated. Hetero atoms are non-carbon atoms, for instance N, O, S or P atoms. Alkyl or alkylene interrupted by hetero groups such as oxygen or cycloalkylene may be interrupted by one or more of these groups as long as no linkages of the type Oxe2x80x94O, Oxe2x80x94N etc. occur.
The index s is the valency of A; for example, A as alkyl is a monovalent, A as alkylene a divalent, A as alkanetriyl a trivalent, A as alkanetetryl a tetravalent, A as alkanepentayl a pentavalent, A as alkanehexayl a hexavalent, A as alkaneheptayl a heptavalent, and A as alkaneoctayl an octovalent saturated hydrocarbon residue. A residue which is interrupted is interrupted in a carbonxe2x80x94carbon single bond. A residue which is interrupted and/or substituted may be a residue interrupted in one or more carbonxe2x80x94carbon single bonds by one or more divalent interrupting groups, a residue substituted by one or more monovalent substituents, or a residue which is both interrupted in one or more carbonxe2x80x94carbon single bonds by one or more divalent interrupting groups and substituted by one or more monovalent substituents.
Thus, examples for A as C3-C15alkylene substituted by one or more OH and/or interrupted by oxygen, phenylene, C1-C4alkylphenylene, xe2x80x94COOxe2x80x94, xe2x80x94CONHxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94 include groups of the formulae CH2CH(OH)CH2, CH2xe2x80x94C(CH2OH)2xe2x80x94CH2, (CH2)2xe2x80x94N(CHO)xe2x80x94(CH2)2, (CH2)2xe2x80x94N Hxe2x80x94(CH2)2, (CH2)2xe2x80x94Oxe2x80x94(CH2)2, (CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2, CH2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94Oxe2x80x94COxe2x80x94CH2, CH2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)6xe2x80x94Oxe2x80x94COxe2x80x94CH2, CH2xe2x80x94COxe2x80x94Oxe2x80x94(CH2)2xe2x80x94Oxe2x80x94COxe2x80x94CH2.
Halogen is preferably chloro or bromo, especially chloro.
C6-C12aryl is preferably phenyl or naphthyl, especially phenyl.
The compounds of the invention can be pure or mixtures of compounds.
R1 R2, R3, R4, R5, R10 as alkyl are, within the definitions given, for example methyl, ethyl, propyl such as n- or isopropyl, butyl such as n-, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
R8, R9, R12, R13, R14, R15, Rxe2x80x215 and R28-R33 as alkylene are, within the definitions given, for example methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene, 1,2-propylene, 1,1-propylene, 2,2-propylene, 1,4-butylene, 1,3-butylene, 1,2-butylene, 1,1-butylene, 2,2-butylene, 2,3-butylene, or xe2x80x94C5H10xe2x80x94, xe2x80x94C6H12xe2x80x94, C7H14, xe2x80x94C8H16xe2x80x94, xe2x80x94C9H18xe2x80x94, xe2x80x94C10H2Oxe2x80x94, xe2x80x94C11H22xe2x80x94, xe2x80x94C12H24xe2x80x94, xe2x80x94C13H26xe2x80x94, xe2x80x94C14H28xe2x80x94, xe2x80x94C15H30xe2x80x94, xe2x80x94C16H32xe2x80x94, xe2x80x94C17H34-, xe2x80x94C18H36xe2x80x94.
R8, R9 and R28-R33 are especially preferred as methylene.
In R5, R10, R11 as C5-C12cycloalkyl or cycloalkoxy, the cycloalkyl part is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl. C5-C12-Cycloalkenyl includes cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl.
C1-C4alkyl or akloxy substituted cycloalkyl or phenyl (containing mainly 1-3, e.g. 1 or 2 alkyl groups) include inter alia 2- or 4-methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, t-butylcyclohexyl, methylphenyl, methoxyphenyl, dimethylphenyl.
Phenylalkyl or phenylalkoxy are alkyl or alkoxy each of which is substituted by phenyl. R5, R10 as phenylalkyl or phenylalkoxy are, within the definitions given, for example benzyl, benzyloxy, xcex1-methylbenzyl, xcex1-methylbenzyloxy, cumyl, cumyloxy.
R5 and R10 as alkanoyl are, for example, formyl, acetyl, propionyl, butyryl, pentanoyl, octanoyl; R5 as alkanoyl is preferred as C2-C8alkanoyl, especially acetyl.
Residues alkenoyl, such as in the definition of R5, are most preferably acryloyl or methacryloyl.
Residues alkenyl, such as in the definition of R5, are most preferably allyl.
X is preferably NH; X1-X6 are most preferably O; Z is most preferred as N(R10)2; i is most preferred as zero.
The index p is preferably from the range 2-6.
A preferred blend of polycarbonate with acrylonitrile-butadiene-styrene terpolymer (component (A) of the above composition) is a blend of 10 to 90 parts by weight of polycarbonate with 90 to 10 parts by weight of acrylonitrile-butadiene-styrene terpolymer.
Polycarbonates contained in these blends are to be understood as being especially those polymers the constitutional repeating unit of which corresponds to the formula 
wherein W is a divalent phenolic radical. Examples of W are given inter alia in U.S. Pat. No. 4,960,863 and DE-A-3922496. W can be derived, for example, from hydroquinone, resorcinol, dihydroxybiphenylene or bisphenols in the broadest sense of the term, such as bis(hydroxyphenyl)alkanes, cycloalkanes, sulfides, ethers, ketones, sulfones, sulfoxides, xcex1,xcex1xe2x80x2-bis(hydroxyphenyl)diisopropylbenzenes, for example the compounds 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, or from the bisphenols of the formulae 
The composition of the invention preferably contains as further component (C) a UV absorber from the class of the benzotriazoles, o-hydroxyphenyl-s-triazines and/or benzophenones, examples of which are listed below.
Preferred is composition, wherein in the compound of formula I (component B)
s is from the range 2 to 6;
when s is 2
A is C2-C10alkylene; C3-C12alkylene substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or a group of the formula xe2x80x94R8xe2x80x94COOxe2x80x94R12xe2x80x94OCOxe2x80x94R9xe2x80x94 (IIa);
when s is 3,
A is a group of the formula (IIIa) 
when s is 4,
A is one of the groups of the formulae (IVa) or (IVd) 
when s is 5,
A is a group of the formula (Va) 
when s is 6,
A is one of the groups of the formulae (VIb)-(VIf) 
the index i is zero or 1;
R1, R2, R3 and R4, independently of each other, are methyl;
R5 is hydrogen; C1-C18alkyl; oxyl; OH; C1-C18alkoxy; C5-C12cycloalkoxy; C3-C8alkenyl; or R5 is C1-C8alkanoyl; C3-C5alkenoyl; C1-C18alkanoyloxy; glycidyl; or a group xe2x80x94CH2CH(OH)xe2x80x94G, in which G is hydrogen, methyl or phenyl;
R8 and R9, and R28, R29, R30, R31, R32 and R33, independently of each other, are methylene;
R10 is C1-C8alkyl, C1-C8alkanoyl, C5-C12cycloalkyl;
R12 is C2-C10alkylene; or C3-C12alkylene interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R15 and Rxe2x80x215, independently of each other, are is C2-C10alkylene;
R17 is C4-C10alkantetryl;
R18 is C5-C10alkanepentayl;
X is xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94N(R0)xe2x80x94;
X1, X2, X3, X4, X5, X6, X7 and X8, independently of each other, are xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94; and
Z stands for NHR10, N(R10)2 or C1-C4alkoxy.
Many compounds of the above component B are novel. The invention therefore also relates to a compound of the formula (Ixe2x80x2) or (II) 
wherein p is from the range 1-10;
s is from the range 1 to 8, preferably 2 to 8;
R1, R2, R3 and R4, independently of each other, are C1-C4alkyl;
R5 is hydrogen; C1-C18alkyl; oxyl; OH; CH2CN; C1-C18alkoxy; C5-C12cycloalkoxy; C3-C3alkenyl; C3-C8alkynyl; C7-C12phenylalkyl; C7-C15phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; C7-C15phenylalkoxy; C7-C15phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; or R5 is C1-C8alkanoyl; C3-C5alkenoyl; C1-C18alkanoyloxy; glycidyl; or a group xe2x80x94CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl;
when s is 1, A is C2-C18alkylene substituted by OR30, wherein R30 is C1-C8alkyl or C1-C8alkanoyl substituted by a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C1-C4alkyl and/or C1-C18alkoxy;
when s is 2
A is C3-C15alkylene substituted by one or more OH and/or interrupted by one or more oxygen, phenylene, C1-C4alkylphenylene, xe2x80x94COOxe2x80x94, xe2x80x94CONHxe2x80x94, 
xe2x80x83xe2x80x94NHxe2x80x94 and/or xe2x80x94NR10xe2x80x94; or A is C4-C12alkenylene;
and when R5 is not hydrogen, A also embraces C2-C10alkylene; C2-C10alkylene interrupted by phenylene or C1-C4alkylphenylene;
when s is 3,
A is C3-C10alkantriyl; C3-C12alkantriyl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (IIIa)-(IIId) 
when s is 4,
A is C4-C10alkantetryl; C4-C12alkantetryl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (IVa)-(IVd) 
when s is 5,
A is C5-C10alkanepentayl; C5-C12alkanepentayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (Va)-(Vc) 
when s is 6,
A is C6-C10alkanehexayl; C6-C12alkanehexayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (VIa)-(VIf) 
when s is 7,
A is C7-C10alkaneheptayl; C7-C12alkaneheptayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (VIIa)-(VIId) 
when s is 8,
A is C8-C10alkaneoctayl; C8-C12alkaneoctayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or one of the groups of the formulae (VIIIa)-(VIIIb) 
the index i is zero or 1;
R8 and R9, and R28, R29, R30, R31, R32 and R33, independently of each other, are methylene, and when R5 is not hydrogen, additionally embrace ethylene;
R10 is C1-C8alkyl, C1-C8alkanoyl, C5-C12cycloalkyl, C7-C15phenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C1-C4alkyl and C1-C4alkoxy;
R12, R13 and R14, independently of each other, are C2-C10alkylene; C3-C12alkylene substituted by OH and/or interrupted by oxygen, phenylene, C1-C4alkylphenylene, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; C4-C12alkenylene;
R15 and Rxe2x80x215, independently of each other, are is C2-C10alkylene; C3-C12alkylene substituted by OH and/or interrupted by oxygen, phenylene, C1-C4alkylphenylene, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R16 is C3-C10alkantriyl; C3-C12alkantriyl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R17 is C4-C10alkantetryl; C4-C12alkantetryl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R18 is C5-C10alkanepentayl; C5-C12alkanepentayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R19 is C6-C10alkanehexayl; C6-C12alkanehexayl substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
X is xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94N(R10)xe2x80x94;
X1, X2, X3, X4, X5, X6, independently of each other, are xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94;
Y is xe2x80x94Oxe2x80x94 or a residue of the formula 
Z stands for halogen, NH2, NHR10, N(R10)2 or C1-C4alkoxy;
Z1 has one of the meanings given for Z or is xe2x80x94Xxe2x80x94Rxe2x80x215xe2x80x94XH and
Z2 is H or a residue of the formula 
Preferred meanings in the formula (Ixe2x80x2) include those given above for formula (I), where appropriate.
Also preferred is a compound of the formula (Ixe2x80x2) or (II) wherein p is from the range 2-6, s is from the range 2 to 8;
R1, R2, R3 and R4, independently of each other, are methyl or ethyl;
R5 is hydrogen; C1-C18alkyl; oxyl; OH; CH2CN; C1-C18alkoxy; C5-C12cycloalkoxy; C3-C8alkenyl; C7-C12phenylalkyl; C7-C15phenylalkoxy; or R5 is C1-C6alkanoyl; C3-C5alkenoyl; C1-C18alkanoyloxy; glycidyl; or a group xe2x80x94CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl;
when s is 2
A is C3-C12alkylene substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; C4-C12alkenylene; or one of the groups of the formulae (IIa)-(IIe) 
and when R5 is not hydrogen, A also embraces C2-C10alkylene; C2-C10alkylene interrupted by phenylene or C1-C4alkylphenylene;
when s is 3,
A is C3-C10alkantriyl; or one of the groups of the formulae (IIIa)-(IIId) 
when s is 4,
A is C4-C10alkantetryl; or one of the groups of the formulae (IVa)-(IVd) 
when s is 5,
A is C5-C10alkanepentayl; or a group of the formula (Va) 
when s is 6,
A is C6-C10alkanehexayl; or one of the groups of the formulae (VIb)-(VIf) 
when s is 7,
A is C7-C10alkaneheptayl;
when s is 8,
A is C8-C10alkaneoctayl; or one of the groups of the formulae (VIIIa)-(VIIIb);
the index i is zero or 1;
R8 and R9, and R28, R29, R30, R31, R32 and R33, independently of each other, are methylene;
R10 is C1-C8alkyl, C1-C8alkanoyl, C5-C12cycloalkyl, C7-C15phenylalkyl;
R12, R13 and R14, independently of each other, are C2-C10alkylene; C3-C12alkylene substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; C4-C12alkenylene;
R15 and Rxe2x80x215, independently of each other, are is C2-C10alkylene; C3-C12alkylene substituted by OH and/or interrupted by oxygen, phenylene, C1-C4alkylphenylene, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R16 is C3-C10alkantriyl;
R17 is C4-C10alkantetryl;
R18 is C5-C10alkanepentayl;
X is xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94N(R10)xe2x80x94;
X1, X2, X3, X4, X5, independently of each other, are xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94; and
Z stands for halogen, NH2, NHR10, N(R10)2 or C1-C4alkoxy.
Especially preferred is a compound of the formula (Ixe2x80x2) wherein s is from the range 2 to 6;
R1, R2, R3 and R4, independently of each other, are methyl or ethyl;
R5 is hydrogen; C1-C18alkyl; oxyl; OH; CH2CN; C1-C18alkoxy; C5-C12cycloalkoxy; C3-C8alkenyl; C7-C12phenylalkyl; C7-C15phenylalkoxy; or R5 is C1-C8alkanoyl; C3-C5alkenoyl; C1-C18alkanoyloxy; glycidyl; or a group xe2x80x94CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl;
when s is 2
A is C3-C12alkylene substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; C4-C12alkenylene; or a group of the formula (IIa)
xe2x80x94R8xe2x80x94COOxe2x80x94R12xe2x80x94OCOxe2x80x94R9xe2x80x94;xe2x80x83xe2x80x83(IIa) 
and when R5 is not hydrogen, A also embraces C2-C10alkylene;
when s is 3,
A is C3-C10alkantriyl; or one of the groups of the formulae (IIIa), (IIIb) or (IIId);
when s is 4,
A is C4-C10alkantetryl; or one of the groups of the formulae (IVa), (IVb) or (IVd);
when s is 5,
A is C5-C10alkanepentayl;
when s is 6,
A is one of the groups of the formulae (VIb)-(VIf);
the index i is zero or 1;
R8 and R9, and R28, R29, R30, R31, R32 and R33, independently of each other, are methylene;
R10 is C1-C8alkyl, C1-C8alkanoyl, C5-C12cycloalkyl; R12 is C2-C10alkylene; C3-C12alkylene substituted by OH and/or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94;
R15 and Rxe2x80x215, independently of each other, are is C2-C10alkylene;
R16 is C3-C10alkantriyl;
R17 is C4-C10alkantetryl;
X is xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94N(R10)xe2x80x94;
X1, X2, X3, X4, independently of each other, are xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94; and
Z stands for NHR10 or N(R10)2.
Most preferred is a compound of the formula (Ixe2x80x2) wherein s is 2, 3, 4 or 6;
R1, R2, R3 and R4 are methyl;
R5 is hydrogen; C1-C8alkyl; C1-C18alkoxy; cyclohexyloxy; allyl; benzyl; acetyl; C3-C4alkenoyl; glycidyl;
when s is 2
A is C3-C10alkylene substituted by OH or interrupted by oxygen, xe2x80x94NHxe2x80x94 or xe2x80x94NR10xe2x80x94; or a group of the formula xe2x80x94R8xe2x80x94COOxe2x80x94R12xe2x80x94OCOxe2x80x94R9xe2x80x94 (IIa);
and when R5 is not hydrogen, A also embraces C2-C10alkylene;
when s is 3, A is a group of the formula (IIIa);
when s is 4, A is a group of the formula (IVa) or (IVd);
when s is 6, A is a groups of the formula (VIe);
the index i is zero;
R8 and R9, and R28, R29, R30, R31, R32 and R33 are methylene;
R10 is C1-C8alkyl, formyl, acetyl, or cyclohexyl;
R12 is C2-C10alkylene; or C3-C10alkylene interrupted by oxygen;
R15 and Rxe2x80x215, independently of each other, are is C2-C10alkylene;
R17 is C4-C10alkantetryl;
X is xe2x80x94NHxe2x80x94;
X1, X2, X3, X4 are xe2x80x94Oxe2x80x94; and
Z stands for N(R10)2.
The preparation of compounds of the formula I or Ixe2x80x2 can start from the compound 3,3,5,5-tetraalkyl-piperazin-2,6-dione and can follow or be carried out in analogy to methods described in the documents cited on page 1 or standard procedures described in textbooks of organic chemistry; examples for such methods are alkylation, (trans)esterification or etherification, substitution etc.
Compounds thus obtained may be further derivatized by applying suitable synthetic methods known in the art, e.g. in analogy to methods described in EP-A-375612, U.S. Pat. No. 5,204,473, U.S. Pat. No. 5,004,770, and Kurumada et al., J. Polym. Sci., Poly. Chem. Ed. 23,1477 (1985), as well as U.S. Pat. No. 5,449,776, example 8, and publications cited therein, for the modification of piperidine derivatives.
The novel compounds of present invention can be employed with advantage for stabilizing organic material against the damaging effect of light, oxygen and/or heat. They are notable for high substrate compatibility and good persistence in the substrate.
Examples of materials to be stabilized in accordance with the invention are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either xcfx80- or "sgr"-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(xcex1-methylstyrene).
6. Copolymers of styrene or xcex1-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
7. Graft copolymers of styrene or xcex1-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from xcex1,xcex2-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
The invention therefore also provides compositions comprising
A) an organic material which is sensitive to oxidative, thermal and/or actinic degradation, and
B) at least one compound of the formula Ixe2x80x2, and provides for the use of compounds of the formula Ixe2x80x2 for stabilizing organic material against oxidative, thermal or actinic degradation.
Effects of degradation inter alia may be discoloration, molecular breakdown or buildup. Thus, the invention likewise embraces a method of stabilizing organic material against thermal, oxidative and/or actinic breakdown/buildup, which comprises applying or adding at least one compound of the formula Ixe2x80x2 to this material.
In general, the compounds of the formula I or Ixe2x80x2 are added to the material to be stabilized in amounts of from 0.1 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2% (based on the material to be stabilized). Particular preference is given to the use of the novel compounds in amounts of from 0.05 to 1.5%, especially from 0.1 to 0.5%.
In addition to the compounds of the formula I or Ixe2x80x2, the novel compositions may as additional component C comprise one or more conventional additives such as, for example, those indicated below.
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(xcex1-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1xe2x80x2-methylundec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methylheptadec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methyltridec-1xe2x80x2-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and alkylated hydrocuinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octa-decyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
1.4. Tocopherols, for example xcex1-tocopherol, xcex2-tocopherol, xcex3-tocopherol, xcex4-tocopherol and mixtures thereof (Vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2xe2x80x2-thiobis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-thiobis(4-octylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-3-methylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-2-methylphenol), 4,4xe2x80x2-thiobis-(3,6-di-sec-amylphenol), 4,4xe2x80x2-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
1.6. Alkylidenebisphenols, for example 2,2xe2x80x2-methylenebis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-methylenebis(6-tert-butyl-4-ethylphenol), 2,2xe2x80x2-methylenebis[4-methyl-6-(xcex1-methylcyclohexyl)phenol], 2,2xe2x80x2-methylenebis(4-methyl-6-cyclohexylphenol), 2,2xe2x80x2-methylenebis(6-nonyl-4-methylphenol), 2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2xe2x80x2-methylenebis[6-(xcex1-methylbenzyl)-4-nonylphenol], 2,2xe2x80x2-methylenebis[6-(xcex1,xcex1-dimethylbenzyl)-4-nonylphenol], 4,4xe2x80x2-methylenebis (2,6-di-tert-butylphenol), 4,4xe2x80x2-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3xe2x80x2-tert-butyl-4xe2x80x2-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. O-, N- and S-benzyl compounds, for example 3,5,3xe2x80x2,5xe2x80x2-tetra-tert-butyl-4,4xe2x80x2-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercaptoethyl-2,2-bis-3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of D-(3,5-di-tert-butyl-4-hydroxyphenyl)prolionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of P-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of D-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of B-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,Nxe2x80x2-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard(copyright)XL-1 supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,Nxe2x80x2-di-isopropyl-p-phenylenediamine, N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-methylheptyl)-p-phenylenediamine, N,Nxe2x80x2-dicyclohexyl-p-phenylenediamine, N,Nxe2x80x2-diphenyl-p-phenylenediamine, N,Nxe2x80x2-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1-methylheptyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-cyclohexyl-Nxe2x80x2-phenyl-p-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyidiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,pxe2x80x2-di-tert-octyidiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4xe2x80x2-diaminodiphenylmethane, 4,4xe2x80x2-diaminodiphenylmethane, N,N,Nxe2x80x2,Nxe2x80x2-tetramethyl-4,4xe2x80x2-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguamide, bis[4-(1xe2x80x2,3xe2x80x2-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-und dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono-und dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono-und dialkylated tert-octyl-phenothiazines, N-allylphenothiazin, N,N,Nxe2x80x2,Nxe2x80x2-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV Absorbers and Light Stabilisers
2.1.2-(2xe2x80x2-Hydroxyphenyl)benzotriazoles, for example 2-(2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-5xe2x80x2-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-sec-butyl-5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-4xe2x80x2-octyloxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-amyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-bis-(xcex1,xcex1-dimethylbenzyl)-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)-carbonylethyl]-2xe2x80x2-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)carbonylethyl]-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2-dodecyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2xe2x80x2-methylene-bis-[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3xe2x80x2-tert-butyl-5xe2x80x2-(2-methoxycarbonylethyl)-2xe2x80x2-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [Rxe2x80x94CH2CH2xe2x80x94COOxe2x80x94CH2CH2"Brketclosest"2 where R=3xe2x80x2-tert-butyl-4xe2x80x2-hydroxy-5xe2x80x2-2H-benzotriazol-2-ylphenyl, 2-[2xe2x80x2-hydroxy-3xe2x80x2-(xcex1,xcex1-dimethylbenzyl)-5xe2x80x2-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole; 2-[2xe2x80x2-hydroxy-3xe2x80x2-(1,1,3,3-tetramethylbutyl)-5xe2x80x2-(xcex1,xcex1-dimethylbenzyl)phenyl]benzotriazole.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2xe2x80x2,4xe2x80x2-trihydroxy and 2xe2x80x2-hydroxy-4,4xe2x80x2-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, isooctyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, methyl xcex1-carbomethoxycinnamate, methyl xcex1-cyano-xcex2-methyl-p-methoxy-cinnamate, butyl xcex1-cyano-xcex2-methyl-p-methoxy-cinnamate, methyl xcex1-carbomethoxy-xcex2-methoxycinnamate and N-(xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2xe2x80x2-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1xe2x80x2-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N,Nxe2x80x2-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,Nxe2x80x2-bis-formyl-N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxy-methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction product of maleic acid anhydride-xcex1-olefin-copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
2.7. Oxamides, for example 4,4xe2x80x2-dioctyloxyoxanilide, 2,2xe2x80x2-diethoxyoxanilide, 2,2xe2x80x2-dioctyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2,2xe2x80x2-didodecyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2-ethoxy-2xe2x80x2-ethyloxanilide, N,Nxe2x80x2-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2xe2x80x2-ethoxanilide and its mixture with 2-ethoxy-2xe2x80x2-ethyl-5,4xe2x80x2-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1.3.5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
3. Metal deactivators, for example N,Nxe2x80x2-diphenyloxamide, N-salicylal-Nxe2x80x2-salicyloyl hydrazine, N,Nxe2x80x2-bis(salicyloyl) hydrazine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,Nxe2x80x2-diacetyladipoyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)oxalyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4xe2x80x2-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2xe2x80x2,2xe2x80x3-nitrilo[triethyltris(3,3xe2x80x2,5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite], 2-ethylhexyl(3,3xe2x80x2,5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite.
Especially preferred are the following phosphites:
Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos(copyright)168, Ciba-Geigy), tris(nonylphenyl) phosphite, 
5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Thiosynergists, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavengers, for example esters of xcex2-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(xcex2-dodecylmercapto)propionate.
9. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zink pyrocatecholate.
11. Nucleating agents, for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).
12. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3xe2x80x2-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
The conventional additives are judiciously employed in amounts of 0.1-10% by weight, for example 0.2-5% by weight, based on the material to be stabilized.
Costabilizers optionally to be added to the stabilizer mixture of the invention are preferably further light stabilizers, for instance those of the 2-hydroxyphenyl-benztriazole, 2-hydroxyphenyl-triazine, benzophenone or oxalanilide classes, e.g. as described in EP-A-453396, EP-A-434608, U.S. Pat. No. 5,298,067, WO 94/18278, GB-A-2297091 and WO 96/28431, and/or further hindered amines derived from 2,2,6,6-tetraalkylpiperidine containing at least one group of the formula 
in which G is hydrogen or methyl, especially hydrogen; examples of tetraalkylpiperidine derivatives which can be used as costabilizers with mixtures of the invention are given in EP-A-356 677, pages 3-17, sections a) to f). These sections of this EP-A are regarded as part of the present description.
Especially preferred as costabilizers are 2-hydroxyphenyl-benztriazoles and/or 2-hydroxyphenyl-triazines.
Of particular interest is the use of compounds of the formula Ixe2x80x2 as stabilizers in synthetic organic polymers, especially thermoplastic polymers, and corresponding compositions, in film forming binders for coatings and in reprographic material.
The organic materials to be protected are preferably natural, semisynthetic or, preferably, synthetic organic materials. Particular preference is given to synthetic organic polymers or mixtures of such polymers, especially thermoplastic polymers such as polyolefins, especially polyethylene and polypropylene (PP), and coating compositions. Of special importance are also polycarbonates and blends thereof, for example the polymers listed above under items 19 and 28.
Incorporation into the materials can be effected, for example, by mixing in or applying the compounds of the formula Ixe2x80x2 and, if desired, further additives by the methods which are customary in the art. Where polymers are involved, especially synthetic polymers, incorporation can take place prior to or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices. A further possibility for incorporating the compounds of the formula Ixe2x80x2 into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking. In this context the compound of the formula can be added as it is or else in encapsulated form (for example in waxes, oils or polymers). In the case of addition prior to or during the polymerization, the compounds of the formula Ixe2x80x2 can also act as a regulator of the chain length of the polymers (chain terminator).
The compounds of the formula I or Ixe2x80x2 can also be added in the form of a masterbatch containing said compound in a concentration, for example, of from 2.5 to 25% by weight to the polymers that are to be stabilized.
The compounds of the formula I or Ixe2x80x2 can judiciously be incorporated by the following methods:
as emulsion or dispersion (e.g. to latices or emulsion polymers),
as a dry mixture during the mixing in of additional components or polymer mixtures,
by direct introduction into the processing apparatus (e.g. extruders, internal mixers, etc),
as solution or melt.
Novel polymer compositions can be employed in various forms and/or processed to give various products, for example as (to give) films, fibres, tapes, moulding compositions, profiles, or as binders for coating materials, adhesives or putties.
Other materials to be stabilized according to the invention are recording materials. By such materials are meant, for example, those described in Research Disclosure 1990, 31429 (pages 474-480) for photographic reproduction and other reprographic techniques.
The novel recording materials comprise, for example, those for pressure-sensitive copying systems, microcapsule photocopier systems, heat-sensitive copier systems, photographic material and ink-jet printing.
The novel photographic material can be a black and white or a colour photographic material; colour photographic material is preferred. Further details on the structure of colour photographic material, and the components which can be employed in the novel material, can be found, inter alia, in U.S. Pat. No. 5,538,840, column 27, line 25, to column 106, line 16, and in the publications cited therein; these passages of U.S. Pat. No. 5,538,840 are hereby incorporated by reference. Application of the novel stabilizers of the formula Ixe2x80x2 is essentially as described for UV absorbers or hindered amine stabilizers in this reference.
Further important components, especially couplers, are described in U.S. Pat. No. 5,578,437. Likewise of particular interest is the use of the novel mixtures comprising compounds of the formula (I) as stabilizers for coatings, for example for paints. The invention therefore also relates to those compositions whose component (A) is a film-forming binder for coatings. The novel coating composition preferably comprises 0.01-10 parts by weight of (B), in particular 0.05-10 parts by weight of (B), especially 0.1-5 parts by weight of (B), per 100 parts by weight of solid binder (A).
Multilayer systems are possible here as well, where the concentration of the novel stabilizer (component (B)) in the outer layer can be relatively high, for example from 1 to 15 parts by weight of (B), in particular 3-10 parts by weight of (B), per 100 parts by weight of solid binder (A).
The use of the compounds of the formula I or Ixe2x80x2 in coatings is accompanied by the additional advantage that it prevents delamination, i.e. the flaking-off of the coating from the substrate. This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates.
The binder (component (A)) can in principle be any binder which is customary in industry, for example those described in Ullmann""s Encyclopedia of Industrial Chemistry, 5th edition, Vol. A18, pp. 368-426, VCH, Weinheim 1991. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, predominantly on a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.
Component (A) can be a cold-curable or hot-curable binder; the addition of a curing catalyst may be advantageous. Suitable catalysts which accelerate curing of the binder are described, for example, in Ullmann""s Encyclopedia of Industrial Chemistry, Vol. A18, p.469, VCH Verlagsgesellschaft, Weinheim 1991.
Preference is given to coating compositions in which component (A) is a binder comprising a functional acrylate resin and a crosslinking agent.
Examples of coating compositions containing specific binders are:
1. paints based on cold- or hot-crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, if desired with addition of a curing catalyst;
2. two-component polyurethane paints based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
3. one-component polyurethane paints based on blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during baking, if desired with addition of a melamine resin;
4. one-component polyurethane paints based on a trisalkoxycarbonyltriazine crosslinker and a hydroxyl group containing resin such as acrylate, polyester or polyether resins;
5. one-component polyurethane paints based on aliphatic or aromatic urethaneacrylates or polyurethaneacrylates having free amino groups within the urethane structure and melamine resins or polyether resins, if necessary with curing catalyst;
6. two-component paints based on (poly)ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
7. two-component paints based on (poly)ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester;
8. two-component paints based on carboxyl- or amino-containing polyacrylates and polyepoxides;
9. two-component paints based on acrylate resins containing anhydride groups and on a polyhydroxy or polyamino component;
10. two-component paints based on acrylate-containing anhydrides and polyepoxides;
11. two-component paints based on (poly)oxazolines and acrylate resins containing anhydride groups, or unsaturated acrylate resins, or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
12. two-component paints based on unsaturated polyacrylates and polymalonates;
13. thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins;
14. paint systems based on siloxane-modified or fluorine-modified acrylate resins;
15. paint systems, especially for clearcoats, based on malonate-blocked isocyanates with melamine resins (e.g. hexamethoxymethylmelamine) as crosslinker (acid catalyzed);
16. UV-curable systems based on oligomeric urethane acrylates, or oligomeric urethane acrylates in combination with other oligomers or monomers;
17. dual cure systems, which are cured first by heat and subsequently by UV or electron irradiation, or vice versa, and whose components contain ethylenic double bonds capable to react on irradiation with UV light in presence of a photoinitiator or with an electron beam.
In addition to components (A) and (B), the coating composition according to the invention preferably comprises as component (C) a known light stabilizer of the sterically hindered amine type, the 2-(2-hydroxyphenyl)-1,3,5-triazine and/or 2-hydroxyphenyl-2H-benzotriazole type as explained above, examples are mentioned in the above list in sections 2.1, 2.6 and 2.8. Further examples for light stabilizers of the 2-(2-hydroxyphenyl)-1,3,5-triazine type advantageously to be added can be found e.g. in the publications U.S. Pat. No. 4,619,956, EP-A-434608, U.S. Pat. No. 5,198,498, U.S. Pat. No. 5,322,868, U.S. Pat. No. 5,369,140, U.S. Pat. No. 5,298,067, WO-94/18278, EP-A-704437, GB-A-2297091, WO-96/28431. Of special technical interest is the addition of the 2-(2-hydroxyphenyl)-1,3,5-triazines and/or 2-hydroxyphenyl-2H-benzotriazoles, especially the 2-(2-hydroxyphenyl)-1,3,5-triazines.
Component (C) is preferably used in an amount of 0.05-5 parts by weight per 100 parts by weight of the solid binder.
Examples of tetraalkylpiperidine derivatives which can be used advantageously as component (C) in coatings are given in EP-A-356 677, pages 3-17, sections a) to f). These sections of this EP-A are regarded as part of the present description. It is particular expedient to employ the following tetraalkylpiperidine derivatives:
bis(2,2,6,6-tetramethylpiperid-4-yl) succinate,
bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,
bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate,
di(1,2,2,6,6-pentamethylpiperid-4-yl) butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate,
tetra(2,2,6,6-tetramethylpiperid-4-yl) butane-1,2,3,4-tetracarboxylate,
tetra(1,2,2,6,6-pentamethylpiperid-4-yl) butane-1,2,3,4-tetracarboxylate,
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane,
8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione,
1,1-bis-(1,2,2,6,6-pentamethylpiperidine-4-yl-oxycarbonyl)-2-(4-methoxyphenyl)ethene,
or a compound of the formulae 
Apart from components (A), (B) and, if used, (C), the coating composition can also comprise further components, examples being solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, drying catalysts and/or levelling agents. Examples of possible components are those described in Ullmann""s Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim 1991.
Possible drying catalysts or curing catalysts are, for example, organometallic compounds, amines, amino-containing resins and/or phosphines. Examples of organometallic compounds are metal carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, especially those of the metals Al, Ti or Zr, or organometallic compounds such as organotin compounds, for example.
Examples of metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates or tallates.
Examples of metal chelates are the aluminium, titanium or zirconium chelates of acetylacetone, ethyl acetylacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate, and the alkoxides of these metals.
Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.
Examples of amines are, in particular, tertiary amines, for example tributylamine, triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or diazabicyclooctane (triethylenediamine) and salts thereof. Further examples are quaternary ammonium salts, for example trimethylbenzylammonium chloride.
Amino-containing resins are simultaneously binder and curing catalyst. Examples thereof are amino-containing acrylate copolymers.
The curing catalyst used can also be a phosphine, for example triphenylphosphine.
The novel coating compositions can also be radiation-curable coating compositions. In this case, the binder essentially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds, which after application are cured by actinic radiation, i.e. converted into a crosslinked, high molecular weight form. Where the system is UV-curing, it generally contains a photoinitiator as well. Corresponding systems are described in the abovementioned publication Ullmann""s Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pages 451-453. In radiation-curable coating compositions, the novel stabilizers can also be employed without the addition of sterically hindered amines.
The coating compositions according to the invention can be applied to any desired substrates, for example to metal, wood, plastic or ceramic materials. They are preferably used as topcoat in the finishing of automobiles. If the topcoat comprises two layers, of which the lower layer is pigmented and the upper layer is not pigmented, the novel coating composition can be used for either the upper or the lower layer or for both layers, but preferably for the upper layer.
The novel coating compositions can be applied to the substrates by the customary methods, for example by brushing, spraying, pouring, dipping or electrophoresis; see also Ullmann""s Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 491-500.
Depending on the binder system, the coatings can be cured at room temperature or by heating. The coatings are preferably cured at 50-150xc2x0 C., and in the case of powder coatings or coil coatings even at higher temperatures.
The coatings obtained in accordance with the invention have excellent resistance to the damaging effects of light, oxygen and heat; particular mention should be made of the good light stability and weathering resistance of the coatings thus obtained, for example paints.
The invention therefore also relates to a coating, in particular a paint, which has been stabilized against the damaging effects of light, oxygen and heat by a content of the compound of the formula (I) according to the invention. The paint is preferably a topcoat for automobiles. The invention furthermore relates to a process for stabilizing a coating based on organic polymers against damage by light, oxygen and/or heat, which comprises mixing with the coating composition a mixture comprising a compound of the formula (I), and to the use of mixtures comprising a compound of the formula (I) in coating compositions as stabilizers against damage by light, oxygen and/or heat.
The coating compositions can comprise an organic solvent or solvent mixture in which the binder is soluble. The coating composition can otherwise be an aqueous solution or dispersion. The vehicle can also be a mixture of organic solvent and water. The coating composition may be a high-solids paint or can be solvent-free (e.g. a powder coating material). Powder coatings are, for example, those described in Ullmann""s Encyclopedia of Industrial Chemistry, 5th Ed., A18, pages 438-444. The powder coating material may also have the form of a powder-slurry (dispersion of the powder preferably in water).
The pigments can be inorganic, organic or metallic pigments. The novel coating compositions preferably contain no pigments and are used as a clearcoat.
Likewise preferred is the use of the coating composition as a topcoat for applications in the automobile industry, especially as a pigmented or unpigmented topcoat of the paint finish. Its use for underlying coats, however, is also possible.
The examples below illustrate the invention further. All parts or percentages, in the examples as in the remainder of the description and in the claims, are by weight, unless stated otherwise. Room temperature denotes a temperature in the range 20-30xc2x0 C., unless stated otherwise. Data given for elemental analysis are in % by weight calculated (cal) or experimentally measured (exp) for the elements C, H and N. In the examples, the following abbreviations are used: